CN102168242A - Method for preparing colorful titanium dioxide film on surface of porous NiTi alloy at low temperature - Google Patents
Method for preparing colorful titanium dioxide film on surface of porous NiTi alloy at low temperature Download PDFInfo
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- CN102168242A CN102168242A CN 201110093880 CN201110093880A CN102168242A CN 102168242 A CN102168242 A CN 102168242A CN 201110093880 CN201110093880 CN 201110093880 CN 201110093880 A CN201110093880 A CN 201110093880A CN 102168242 A CN102168242 A CN 102168242A
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Abstract
The invention discloses a method for preparing a colorful titanium dioxide film on a surface of porous NiTi alloy at low temperature, comprising the following steps: 1. carrying out preprocessing, deoiling, SiC sand paper grinding, mechnical polishing and electrochemical polishing on the surface of the porous NiTi alloy; 2. carrying out hydrothermal treatment on the preprocessed porous NiTi alloy in a high-pressure hydrothermal kettle containing deionized water, wherein the deionized water is 30-70% by volume of the high-pressure hydrothermal kettle, the hydrothermal treatment temperature is 200-300 DEG C, and the processing time lasts for 8-12 hours; and 3. washing, naturally drying or drying at the temperature of 50-80 DEG C, thus obtaining the porous NiTi alloy provided with the colorful titanium dioxide film. the preparation method is simple, ensures low cost, is not influenced by the shape of the porous NiTi alloy, ensures no environment pollution, and can be used for repair and replacement on hard tissues such as bones, joints, artificial fangs and the like, and the bright color of the film can play roles in identification and attractiveness.
Description
Technical field
The present invention relates to a kind of method for preparing colored titanium deoxid film, relate in particular to the method that a kind of porous NiTi alloy surface low-temperature prepares colored titanium deoxid film.
Background technology
In recent decades, the research and development of bio-medical material has obtained the achievement that attracts people's attention, and makes millions of patients obtain rehabilitation, has improved people's quality of life greatly.Wound increase that causes along with science and technology development, aging population and various mishap etc., people are increasing to the demand of bio-medical material and goods thereof.What the present use of human bearing sclerous tissues implant clinically was maximum is medical metal material, as medical stainless steel, cochrome, titanium or titanium alloy and NiTi shape memory alloy, but these materials can not solve problems such as immunity and biomechanical compatibility satisfactorily, belong to bio-inert material as medical metal material, can not form synostosis with tissue, Young's modulus and osseous tissue do not match, make load not be delivered to adjacent bone tissue by planting body well, " stress shielding " phenomenon appears, thereby cause bone regeneration around implant bone resorption to occur, finally cause the loosening and fracture of planting body, cause the plantation failure.
In order to address the above problem, the investigation of materials scholar proposes to develop porous NiTi alloy both at home and abroad.By adjusting the porosity and the pore morphology of porous NiTi shape memory alloy, make the close requirement of satisfying biomechanical compatibility of its Young's modulus and osseous tissue; The compressibility of porous alloy and vesicular structure help growing into of freshman bone tissue, make the fixing more natural, more reliable of implant; Its shape memory effect and unique volume memory effect become simply implantation process, have alleviated patient's misery greatly; Its super-elasticity has ensured the biomechanics compatibility between implant and when injected organism tissue.This shows that porous NiTi alloy has broad application prospects with the embedded material field at the surgery of hard tissue repair such as bone, joint and tooth and replacement.
Behind the porous NiTi alloy implant into body, because of causing its surface-area that is exposed to circulatory mediator, vesicular structure increases, and the pore texture of three-dimensional communication can cause the crevice corrosion effect, makes it be easier to discharge the Ni ion with genotoxic potential than fine and close NiTi alloy.Employing atomic absorption spectrophotometers such as Jiang have been analyzed the Ni release conditions of porous NiTi alloy and fine and close NiTi alloy, find that the Ni ion burst size of porous NiTi exceeds 2 orders of magnitude than fine and close alloy.The moving point of employings such as Li bit polarization curve method carries out the corrosion behavior test to porous NiTi alloy in 37 ℃ of physiological saline and Hank ' s solution, the disruptive potential that found that porous NiTi alloy is lower than fine and close NiTi alloy, and corrosion current is higher than fine and close NiTi alloy, porous NiTi alloy is described owing to the existence of vesicular structure has reduced the corrosion resistance nature of alloy, this certainly will also will promote the Ni ionic to discharge.In order to improve the safety in utilization of porous NiTi alloy, just need carry out surface modification, to suppress or to avoid the stripping of Ni ion and enter human body to porous NiTi alloy.But vesicular structure makes the surface modification difficulty that becomes, and is because hole inside also needs to handle, improper because of being difficult to infiltrate in the hole to laser surface modification that fine and close NiTi alloy adopted, method such as ion implantation.Therefore, can only adopt the good methods of accessibility such as liquid or gas that porous NiTi alloy is carried out surface modification.
TiO
2Film has been proved has excellent erosion resistance, but since the oxide film that alloy surface forms naturally not fine and close, easily peel off and local corrosion take place, thereby can carry out oxide treatment again, to improve its compactness and erosion resistance to the surface.Porous NiTi alloy is heated to more than 500 ℃ and can still will separates out Ni in the NiTi alloy this moment at surface and the even titanium deoxid film of the inner formation of hole
3The Ti phase influences the shape memory effect and the super-elasticity of alloy, has worsened matrix inherent thermomechanical property.
Summary of the invention
The object of the present invention is to provide a kind of porous NiTi alloy surface low-temperature to prepare the method for colored titanium deoxid film, solved the Ni ion stripping that promptly suppresses porous NiTi alloy, do not worsened the problem of the intrinsic heat mechanical property of alloy again.
The present invention is achieved like this, and method steps is:
(1) porous NiTi alloy surface preparation is deoiled, SiC sand papering, mechanical polishing and electrochemical etching;
(2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills deionized water and is carried out hydrothermal treatment consists, deionized water account for high pressure hydro-thermal kettle long-pending 30～70%, the hydrothermal treatment consists temperature is 200～300 ℃, the treatment time is 8～12 hours;
(3) flushing, seasoning or dry under 50 ~ 80 ℃ of conditions promptly obtain to have the porous nickel-titanium alloy of colored titanium deoxid film.
The container portions of described high pressure water heating kettle is made by stainless steel.
Pretreated porous NiTi alloy must be suspended in the high pressure water heating kettle.
The present invention can be on the porous NiTi surface and hole is inner forms even titanium deoxid film, and the film color can be golden yellow, blueness, green, purple etc.This colored titanium deoxid film is nontoxic, is difficult for peeling off, coming off, and can effectively suppress the stripping of Ni ion, and improves solidity to corrosion, wear resistance and the biocompatibility of porous NiTi alloy.
Preparation method of the present invention is simple, and cost is low, is not subjected to the influence of porous NiTi alloy shape, and environmentally safe can be used for hard tissue repair and alternative such as bone, joint and artificial tooth root, and the bright-colored of film can play discriminating and beauty function.
Embodiment
Embodiment one: present embodiment porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film to carry out according to the following steps: the surface preparation of (one) porous NiTi alloy; (2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills working fluid and carried out hydrothermal treatment consists; (3) flushing, drying, i.e. acquisition has the porous nickel-titanium alloy of colored titanium deoxid film.
Present embodiment is on the porous NiTi surface and hole is inner forms even titanium deoxid film, and the film color can be golden yellow, blueness, green, purple etc.This colored titanium deoxid film is nontoxic, is difficult for peeling off, coming off, and can effectively suppress the stripping of Ni ion, and improves solidity to corrosion, wear resistance and the biocompatibility of porous NiTi alloy.
Present embodiment preparation method is simple, and cost is low, is not subjected to the influence of porous NiTi alloy shape, and environmentally safe can be used for hard tissue repair and alternative such as bone, joint and artificial tooth root, and the bright-colored of film can play discriminating and beauty function.
Embodiment two: the difference of present embodiment and embodiment one is: the surface preparation of step () porous NiTi alloy is followed successively by and deoils, SiC sand papering, mechanical polishing and electrochemical etching.Other step and selected parameter are identical with embodiment one.
Embodiment three: the difference of present embodiment and embodiment one is: the container portions of step (two) mesohigh water heating kettle is made by stainless steel.Other step and selected parameter are identical with embodiment one.
Embodiment four: the difference of present embodiment and embodiment one is: seasoning or dry under 50 ~ 80 ℃ of conditions behind the porous NiTi alloy distilled water flushing in the step (three).Other step and selected parameter are identical with embodiment one.
Embodiment five: the difference of present embodiment and embodiment one is: the pretreated porous NiTi alloy in the step (two) must be suspended in the high pressure water heating kettle.Other step and selected parameter are identical with embodiment one.
Embodiment six: the difference of present embodiment and embodiment one is: the working fluid in the step (two) is deionized water or the deionized water that contains a small amount of hydrogen peroxide.Other step and selected parameter are identical with embodiment one.
Embodiment seven: the difference of present embodiment and embodiment one is: the working fluid in step (two) step (two) be high pressure hydro-thermal kettle long-pending 30～70%.Other step and selected parameter are identical with embodiment one.
Embodiment eight: the difference of present embodiment and embodiment seven is: the hydrothermal treatment consists temperature is 200～300 ℃ in the step (two).Other step and selected parameter are identical with embodiment one.
Embodiment nine: the difference of present embodiment and embodiment one is: the hydrothermal treatment consists time is 8～12 hours in the step (two).Other step and selected parameter are identical with embodiment one.
Embodiment nine: present embodiment porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film to carry out according to the following steps: (one) porous NiTi alloy successively through deoil, SiC sand papering, mechanical polishing and electrochemical etching surface preparation; (2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills 30% deionized water and carried out 300 ℃ of hydrothermal treatment consists 24 hours; (3) seasoning behind the porous NiTi alloy distilled water flushing 3 times promptly obtains the porous NiTi alloy of surface coverage titanium dioxide.
The pressure of present embodiment high pressure water heating kettle is 9MPa, and porous NiTi alloy surface and hole inside all cover the thick grass green titanium deoxid film of one deck～50nm, and film surface is level and smooth, and compact structure is firm with matrix bond, is difficult for peeling off, coming off.Through XPS analysis, surperficial Ni content is 1.2at.%, and Ti mainly exists with tetravalence attitude form, also has a spot of three valence states and divalent state.Solidity to corrosion improves 1 more than the order of magnitude than matrix.
Embodiment ten: present embodiment porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film to carry out according to the following steps: (one) porous NiTi alloy successively through deoil, SiC sand papering, mechanical polishing and electrochemical etching surface preparation; (2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills 50% deionized water and carried out 300 ℃ of hydrothermal treatment consists 24 hours; (3) seasoning behind the porous NiTi alloy distilled water flushing 3 times promptly obtains the porous NiTi alloy of surface coverage titanium dioxide.
The pressure of present embodiment high pressure water heating kettle is 9MPa, and porous NiTi alloy surface and hole inside all cover the thick blue titanium deoxid film of one deck～60nm, and film surface is level and smooth, and compact structure is firm with matrix bond, is difficult for peeling off, coming off.Through XPS analysis, surperficial Ni content is 1.0at.%, and Ti mainly exists with tetravalence attitude form, also has a spot of three valence states and divalent state.Solidity to corrosion improves 1 more than the order of magnitude than matrix.
Embodiment 11: present embodiment porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film to carry out according to the following steps: (one) porous NiTi alloy successively through deoil, SiC sand papering, mechanical polishing and electrochemical etching surface preparation; (2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills 70% deionized water and carried out 270 ℃ of hydrothermal treatment consists 8 hours; (3) seasoning behind the porous NiTi alloy distilled water flushing 3 times promptly obtains the porous NiTi alloy of surface coverage titanium dioxide.
The pressure of present embodiment high pressure water heating kettle can reach 12MPa, and porous NiTi alloy surface and hole inside all cover the thick golden yellow titanium deoxid film of one deck～65nm, and film surface is level and smooth, and compact structure is firm with matrix bond, is difficult for peeling off, coming off.Through XPS analysis, surperficial Ni content is 0.2at.%, and Ti mainly exists with tetravalence attitude form, also has a spot of three valence states.Solidity to corrosion improves nearly 2 orders of magnitude than matrix.
Embodiment 11: present embodiment porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film to carry out according to the following steps: (one) porous NiTi alloy successively through deoil, SiC sand papering, mechanical polishing and electrochemical etching surface preparation; (2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills 70% working fluid and carried out 280 ℃ of hydrothermal treatment consists 24 hours; (3) seasoning behind the porous NiTi alloy distilled water flushing 3 times promptly obtains the porous NiTi alloy of surface coverage titanium dioxide.Wherein the working fluid in the step (two) is the deionized water that contains the 5ml hydrogen peroxide.
The pressure of present embodiment high pressure water heating kettle can reach 17.2MPa, and porous NiTi alloy surface and hole inside all cover the thick purple titanium deoxid film of one deck～150nm, and film surface is level and smooth, and compact structure is firm with matrix bond, is difficult for peeling off, coming off.Through XPS analysis, surperficial Ni content is 0.1at%, and Ti mainly exists with tetravalence attitude form, also has three valence states of minute quantity.Solidity to corrosion improves 2 orders of magnitude than matrix.
Claims (3)
1. a porous NiTi alloy surface low-temperature prepares the method for colored titanium deoxid film, it is characterized in that method steps is:
(1) porous NiTi alloy surface preparation is deoiled, SiC sand papering, mechanical polishing and electrochemical etching;
(2) pretreated porous NiTi alloy is put into the high pressure water heating kettle that fills deionized water and is carried out hydrothermal treatment consists, deionized water account for high pressure hydro-thermal kettle long-pending 30～70%, the hydrothermal treatment consists temperature is 200～300 ℃, the treatment time is 8～12 hours;
(3) flushing, seasoning or dry under 50 ~ 80 ℃ of conditions promptly obtain to have the porous nickel-titanium alloy of colored titanium deoxid film.
2. a kind of porous NiTi alloy surface low-temperature according to claim 1 prepares the method for colored titanium deoxid film, it is characterized in that the container portions of described high pressure water heating kettle is made by stainless steel.
3. a kind of porous NiTi alloy surface low-temperature according to claim 1 prepares the method for colored titanium deoxid film, it is characterized in that pretreated porous NiTi alloy must be suspended in the high pressure water heating kettle.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660737A (en) * | 2012-05-31 | 2012-09-12 | 西北有色金属研究院 | TiNb-alloy surface biological activating treatment method |
| CN102856076A (en) * | 2012-09-09 | 2013-01-02 | 西北有色金属研究院 | Method for preparing film electrode with Co-doped NiO nano-sheet array |
| CN108531961A (en) * | 2018-05-10 | 2018-09-14 | 中国科学院宁波材料技术与工程研究所 | Colour film and preparation method thereof, application |
| CN114309649A (en) * | 2021-12-24 | 2022-04-12 | 吉林大学威海仿生研究院 | Novel method for improving corrosion resistance of NiTi alloy melted in laser selection area through heat treatment process |
| CN114309649B (en) * | 2021-12-24 | 2024-05-28 | 吉林大学威海仿生研究院 | Method for improving corrosion resistance of laser selective melting NiTi alloy through heat treatment process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247238A (en) * | 1998-09-09 | 2000-03-15 | 北京航空航天大学 | In-situ preparing of insulating film on surface of marmem |
| CN1905215A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院化学研究所 | Process for preparing TiO2 nanocrystal porous film electrode by low-temp. electrophoresis sedimentation |
-
2011
- 2011-04-14 CN CN2011100938808A patent/CN102168242B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1247238A (en) * | 1998-09-09 | 2000-03-15 | 北京航空航天大学 | In-situ preparing of insulating film on surface of marmem |
| CN1905215A (en) * | 2005-07-26 | 2007-01-31 | 中国科学院化学研究所 | Process for preparing TiO2 nanocrystal porous film electrode by low-temp. electrophoresis sedimentation |
Non-Patent Citations (1)
| Title |
|---|
| 20080430 刘福等 医用NiTi合金的表面改性研究进展 748-752页 1-3 第37卷, 第4期 2 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102660737A (en) * | 2012-05-31 | 2012-09-12 | 西北有色金属研究院 | TiNb-alloy surface biological activating treatment method |
| CN102856076A (en) * | 2012-09-09 | 2013-01-02 | 西北有色金属研究院 | Method for preparing film electrode with Co-doped NiO nano-sheet array |
| CN102856076B (en) * | 2012-09-09 | 2015-08-05 | 西北有色金属研究院 | A kind of preparation method of Co Ni doped O nano-chip arrays membrane electrode |
| CN108531961A (en) * | 2018-05-10 | 2018-09-14 | 中国科学院宁波材料技术与工程研究所 | Colour film and preparation method thereof, application |
| CN114309649A (en) * | 2021-12-24 | 2022-04-12 | 吉林大学威海仿生研究院 | Novel method for improving corrosion resistance of NiTi alloy melted in laser selection area through heat treatment process |
| CN114309649B (en) * | 2021-12-24 | 2024-05-28 | 吉林大学威海仿生研究院 | Method for improving corrosion resistance of laser selective melting NiTi alloy through heat treatment process |
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| CN102168242B (en) | 2012-11-28 |
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